JP2018177917A - Liquid crystal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition that improves the response speed of a liquid crystal display.SOLUTION: A liquid crystal composition contains a cyclohexane compound represented by formula (1) as a first component and a compound represented by formula (2) as a second component (Rand R(e) are an alkyl group substituted at an equatorial position, or the like; X (e) is a halogen atom substituted at an equatorial position; Rand Rare C1-12 alkyl or the like; Xand Xare fluorine or the like; Zand Zare methyleneoxy or the like).SELECTED DRAWING: None

Description

  The present invention relates to a novel cyclohexane compound and a liquid crystal composition containing the compound, and an object thereof is to improve the response speed of the liquid crystal display.

  Liquid crystal that utilizes optical anisotropy (Δn) (sometimes referred to as “Δn” below) and dielectric anisotropy (Δε) (sometimes referred to as “Δε” below) that are characteristic of liquid crystal compounds A large number of display elements have been manufactured so far, and they have been used in watches, calculators, measuring instruments, automobile panels, word processors, electronic notebooks, mobile phones, printers, computers, TVs, and the like. The liquid crystal compound used in this liquid crystal display element has an inherent liquid crystal phase, and the phase form is roughly classified into a nematic phase, a smectic phase and a cholesteric phase. Among them, the nematic phase is most widely used. Among display methods and drive methods used for display devices, the display methods include dynamic scattering type (DS mode), guest / host type (GH mode), and twisted nematic type (TN mode). Super twisted nematic type (STN mode), thin film transistor type (TFT mode) and ferroelectric liquid crystal type (FLC) have been developed. As a driving method, a static driving method, a multiplex driving method, an active matrix driving method, a two-frequency driving method, and the like have been adopted. Recently, three types of TN type, STN type and TFT type have become mainstream. The liquid crystal material used in any display element is required to be stable to moisture, air, heat, light, etc., and exhibits a liquid crystal phase in as wide a temperature range as possible centered on room temperature, and an appropriate dielectric constant anisotropy It is necessary to have characteristics (Δε) and refractive index anisotropy (Δn), high response speed, and low voltage driving capability. In order to satisfy this property, a liquid crystal having a low viscosity and a low threshold voltage is required. At present, there is no substance which satisfies all the above conditions in a single compound, and several to several tens of liquid crystal compounds are mixed to meet the required characteristics. Furthermore, for the display etc. corresponding to high definition TVs and 3D in recent years, further improvement of the response speed is required.

  Many proposals have also been made for nematic liquid crystal compositions having excellent responsiveness using a cyclohexane compound. For example, the present inventors have previously found that a liquid crystal composition in which a specific cyclohexane compound is mixed improves the response speed of a liquid crystal display, and has filed a patent application (Patent Document 1). Subsequently, the inventors have found that a liquid crystal composition in which a cyclohexane compound having a specific structure is mixed with a nematic liquid crystal having positive dielectric anisotropy remarkably improves the response speed of the liquid crystal display, and obtained a patent (Patent Document 2). Nevertheless, previous techniques have not been fully satisfactory in response speed.

JP 2012-180284 A Patent No. 4669085

  The problem to be solved by the present invention is to provide a liquid crystal composition that improves the response speed of the liquid crystal display.

  The present inventors, who have long studied the liquid crystal composition, have found that the liquid crystal composition in which a low molecular weight compound having a specific steric structure is blended in the mother liquid crystal is a liquid crystal panel with an improved response speed, particularly a TN (Twisted Nematic) system. The present invention has been accomplished by providing a liquid crystal panel with an improved response speed in VA (Vertical Alignment) mode and IPS (In-Plane-Switching) mode.

（式（１）中、Ｒ^１（ｅ），Ｒ^２（ｅ）は、それぞれ同一または異なって、エカトリアル位に置換したＲ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ（ｅ）はエカトリアル位に置換したハロゲン原子を表わす。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物を含有し、
第二成分として、式（２）

（式（２）中、
Ｒ^３、Ｒ^４は独立して水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１１のアルケニルオキシ、又は任意の水素がフッ素で置換された炭素数２から１２のアルキル又はアルケニルであり、
Ｘ^１、Ｘ^２は、独立してフッ素又は塩素であり、
Ｚ^１、Ｚ^２は、独立してメチレンオキシ、カルボニルオキシ、エチレン又は単結合であり、
ｎは、０、１又は２であり、
ｍは、０又は１であり、
ｐは、０、１又は２であり、
ｑは、０、１、２又は３である。）
で表わされる各化合物群の少なくとも１種類の化合物を含有する液晶組成物。
［２］ 第一成分として、痕跡量未満の下記式（３）

（式（３）中、Ｒ^１（ｅ），Ｒ^２（ｅ）は、それぞれ式（１）中におけるＲ^１（ｅ），Ｒ^２（ｅ）と同義であり、Ｘ（ａ）はアキシアル位に置換したハロゲン原子を表わす。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物を含有する、［１］に記載の液晶組成物。
［３］ 下記式（４）

（式（１）中、Ｒ^１，Ｒ^２は、それぞれ同一または異なって、Ｒ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ、Ｙは各々独立に同一又は異なるハロゲン原子を表わす。または、Ｘは酸素原子を表わし、Ｙは該酸素原子への直接結合を表わす。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物を更に含む、
［１］又は［２］に記載の液晶組成物。
［４］ 液晶組成物を製造するための、下記式（１）

（式（１）中、Ｒ^１（ｅ），Ｒ^２（ｅ）は、それぞれ同一または異なって、エカトリアル位に置換したＲ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ（ｅ）はエカトリアル位に置換したハロゲン原子を表わす。）
で表わされるシクロヘキサン化合物の使用。
［５］ 液晶セルに［１］乃至［３］のいずれか一項に記載の液晶組成物が封入されている電気光学表示素子。
［６］ ＴＮ（Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ）方式、ＶＡ（Ｖｅｒｔｉｃａｌ Ａｌｉｇｎｍｅｎｔ）方式、又はＩＰＳ（Ｉｎ−Ｐｌａｎｅ−Ｓｗｉｔｃｈｉｎｇ）方式の液晶パネルである、［５］に記載の電気光学表示素子
［７］ 電気光学表示素子を製造するための、下記式（１）

（式（１）中、Ｒ^１（ｅ），Ｒ^２（ｅ）は、それぞれ同一または異なって、エカトリアル位に置換したＲ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ（ｅ）はエカトリアル位に置換したハロゲン原子を表わす。）
で表わされるシクロヘキサン化合物の使用。 The present invention includes the following.
[1] As the first component, the following formula (1)

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)
Containing at least one compound of the cyclohexane compound group represented by
Formula (2) as a second component

(In the formula (2),
R ³ and R ⁴ independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 11 carbons, or any hydrogen is fluorine And C 2-12 alkyl or alkenyl substituted with
X ¹ and X ² are independently fluorine or chlorine,
Z ¹ and Z ² are independently methyleneoxy, carbonyloxy, ethylene or a single bond,
n is 0, 1 or 2;
m is 0 or 1;
p is 0, 1 or 2;
q is 0, 1, 2 or 3; )
A liquid crystal composition comprising at least one compound of each compound group represented by
[2] The following formula (3) below the trace amount as the first component

(In the formula ^{(3), R 1 (e} ), R 2 (e) is, ^R 1 (e) in each equation ^(1), has the same meaning as ^R 2 (e), X (a) is axial position Represents a halogen atom substituted by
The liquid crystal composition according to [1], comprising at least one compound of a cyclohexane compound group represented by
[3] Following formula (4)

(In formula (1), R ¹ and R ² are the same or different and each represents R, ROCO, RCOO, and R represents an alkyl group, an alkenyl group or an alkynyl group. The alkyl group, alkenyl group or alkynyl group. May be substituted by a halogen atom or a cyano group, and part of CH ₂ groups in the alkyl group, alkenyl group or alkynyl group may be replaced by -O-, -CO- or -COO- X and Y each independently represent the same or different halogen atom, or X represents an oxygen atom, and Y represents a direct bond to the oxygen atom.)
Further comprising at least one compound of the cyclohexane compound group represented by
The liquid crystal composition according to [1] or [2].
[4] The following formula (1) for producing a liquid crystal composition

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)
Use of a cyclohexane compound represented by
[5] An electro-optical display element in which the liquid crystal composition according to any one of [1] to [3] is sealed in a liquid crystal cell.
[6] The electro-optical display device according to [5], which is a liquid crystal panel of TN (Twisted Nematic) system, VA (Vertical Alignment) system, or IPS (In-Plane-Switching) system [7] Electro-optical display device The following formula (1) for producing

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)
Use of a cyclohexane compound represented by

  The liquid crystal composition according to the present invention is excellent in various properties such as viscosity reduction efficiency, thermal stability, and compatibility with a mother liquid crystal, and thus a liquid crystal panel, particularly a TN (Twisted Nematic) system, a VA (Vertical Alignment) system, and When applied to a liquid crystal panel of the IPS (In-Plane-Switching) system, the response speed can be remarkably improved.

It is a figure which shows the NMR data of equatorial-fluorinated derivative (4).

The usage of the terms in this specification is as follows.
The “liquid crystal composition” refers to one or a mixture of two or more compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and one or more compounds having a liquid crystal phase and one or more compounds. It means a mixture of compounds having no liquid crystal phase of
"Liquid crystal display element" means a liquid crystal display panel or a liquid display module.
The “compound of the formula (1)” means one or more compounds represented by the formula (1), and the two or more compounds may be referred to as a compound group. Moreover, the compound which belongs to the compound of Formula (1) may be described as Formula (1-1), Formula (1-2) etc., Furthermore, the compound which belongs to the compound of Formula (1-1) is represented by Formula (1-). It may be described as 1-1), a formula (1-1-2), etc. In addition, without describing as Formula (1), Formula (1-1) etc., Formula may be abbreviated and described only as (1) and (1-1). The same applies to Formula (2) and the following.

1. First component 1.1. Compound of Formula (1) The first component constituting the liquid crystal composition according to the present invention is a cyclohexane compound represented by the following general formula (1). The first component may be a single compound or a mixture of two or more compounds.

（式（１）中、Ｒ^１（ｅ），Ｒ^２（ｅ）は、それぞれ同一または異なって、エカトリアル位に置換したＲ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ（ｅ）はエカトリアル位に置換したハロゲン原子を表わす。）

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)

The compound of formula (1) has, for example, the following configuration.

The number of carbon atoms of R is not particularly limited as long as the performance of the liquid crystal display device is not impaired, but it is preferably C1-12, more preferably C1-8. Examples of the group represented by R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, vinyl, allyl, butenyl, ethynyl, propynyl, butynyl, methoxymethyl, ethoxymethyl and propoxymethyl , Butoxymethyl, methoxyethyl, ethoxyethyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, perfluorovinyl, perfluoroaryl, isopropyl, 1-methylpropyl, 2- Methylpropyl, 2-butylmethyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 1-methylpentyl and the like can be mentioned.
R ¹ and R ² are preferably an unsubstituted alkyl group or an unsubstituted alkenyl group.

  Representative examples of the compound group represented by the formula (1) include compounds of the following formula. However, it is not limited to these compound groups.

Although a plurality of stereoisomers different in the position of X, R ¹ and R ² exist from the compound of the present invention represented by the formula (1), they should be distinguished from the compound of the formula (1) It does not.

  The method for producing the cyclohexane compound of the formula (1) is not particularly limited. For example, it can manufacture by the method of Unexamined-Japanese-Patent No. 2012-180284. The specific method will be described also in Examples described later.

  The content of the cyclohexane compound of the formula (1) in the liquid crystal composition of the present invention is not particularly limited, and an appropriate amount may be selected so as to obtain the desired characteristics. It is preferable to select from the range of 5% to 90% by mass.

（式（３）中、Ｒ^１（ｅ），Ｒ^２（ｅ）は、それぞれ式（１）中におけるＲ^１（ｅ），Ｒ^２（ｅ）と同義であり、Ｘ（ａ）はアキシアル位に置換したハロゲン原子を表わす。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物が痕跡量未満であることが好ましい。 1.2. Compound of Formula (3) The liquid crystal composition according to the present invention contains the following formula (3)

(In the formula ^{(3), R 1 (e} ), R 2 (e) is, ^R 1 (e) in each equation ^(1), has the same meaning as ^R 2 (e), X (a) is axial position Represents a halogen atom substituted by
Preferably, at least one compound of the cyclohexane compound group represented by is less than a trace amount.

The compound of Formula (3) has, for example, the following configuration.

The number of carbon atoms of R, examples of the group represented by R, X, R ¹ and R ² are as described above for the compound of the formula (1).

  The term "less than trace amount" means that the amount is less than the detection limit of a predetermined analytical instrument, and that the liquid crystal composition according to the present invention does not contain the compound of formula (3) at all Although the compound of the formula (3) may be unavoidably mixed in the liquid crystal composition, although it is preferable, in fact, due to technical restrictions due to the synthetic route etc. and economic restrictions associated with the separation and purification treatment etc. The case is also within the scope of the technical idea of the present invention. For example, under the present technical and economic circumstances, the effect of the present invention will be recognized even if the compound of the formula (3) is mixed up to about 100 ppm.

  When producing the cyclohexane compound of Formula (1), the compound of Formula (3) is also often by-produced, but both can be separated and purified by a conventional method. The specific method will be described also in Examples described later.

（式（１）中、Ｒ^１，Ｒ^２は、それぞれ同一または異なって、Ｒ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ、Ｙは各々独立に同一又は異なるハロゲン原子を表わす。または、Ｘは酸素原子を表わし、Ｙは該酸素原子への直接結合を表わす。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物を更に含むことが好ましい。 1.3. Compound of Formula (4) In the liquid crystal composition according to the present invention, a compound represented by the following formula (4)

(In formula (1), R ¹ and R ² are the same or different and each represents R, ROCO, RCOO, and R represents an alkyl group, an alkenyl group or an alkynyl group. The alkyl group, the alkenyl group or the alkynyl group. May be substituted by a halogen atom or a cyano group, and part of CH ₂ groups in the alkyl group, alkenyl group or alkynyl group may be replaced by -O-, -CO- or -COO- X and Y each independently represent the same or different halogen atom, or X represents an oxygen atom, and Y represents a direct bond to the oxygen atom.)
It is preferable to further include at least one compound of the cyclohexane compound group represented by

The number of carbon atoms of R, examples of the group represented by R, X, R ¹ and R ² are as described above for the compound of the formula (1).

The compound of formula (4) has, for example, the following configuration.

  Representative examples of the compound group represented by the formula (4) include compounds of the following formula. However, it is not limited to these compound groups.

  The method for producing the cyclohexane compound of the formula (4) is not particularly limited. For example, it can manufacture by the method of Unexamined-Japanese-Patent No. 2012-180284.

（式（２）中、
Ｒ^３、Ｒ^４は独立して水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１１のアルケニルオキシ、又は任意の水素がフッ素で置換された炭素数２から１２のアルキル又はアルケニルであり、
Ｘ^１、Ｘ^２は、独立してフッ素又は塩素であり、
Ｚ^１、Ｚ^２は、独立してメチレンオキシ、カルボニルオキシ、エチレン又は単結合であり、
ｎは、０、１又は２であり、
ｍは、０又は１であり、
ｐは、０、１又は２であり、
ｑは、０、１、２又は３である。） 2. Second component (mother liquid crystal)
The second component constituting the liquid crystal composition according to the present invention is a compound represented by the following general formula (2). The second component may be a single compound or a mixture of two or more compounds.

(In the formula (2),
R ³ and R ⁴ independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 11 carbons, or any hydrogen is fluorine And C 2-12 alkyl or alkenyl substituted with
X ¹ and X ² are independently fluorine or chlorine,
Z ¹ and Z ² are independently methyleneoxy, carbonyloxy, ethylene or a single bond,
n is 0, 1 or 2;
m is 0 or 1;
p is 0, 1 or 2;
q is 0, 1, 2 or 3; )

Some specific examples of the compound represented by the general formula (2) are as follows.

  The cyclohexane compound (first component) of the present invention constitutes the liquid crystal composition of the present invention by being blended with the second component (mother liquid crystal). The method of formulation is not particularly limited, and can be carried out by a conventional method.

3. Applications The liquid crystal composition of the present invention can be enclosed in a liquid crystal cell to constitute various electro-optical display elements. As the electro-optical display element, for example, dynamic scattering type (DS), guest host type (GH), twisted nematic type (TN, super twisted nematic type (STN), thin film transistor type (TFT), thin film diode type ( Various display modes such as TFD, ferroelectric liquid crystal (FLC), antiferroelectric liquid crystal (AFLC), polymer dispersed liquid crystal (PDLC), vertical alignment (VA), in-plane switching (IPS) Also, various driving methods such as static driving method, time division driving method, active matrix driving method, dual frequency driving method, etc. are applied, in particular, TN (Twisted Nematic) method, VA (Vertical Alignment) method, and IPS When applied to an In-Plane-Switching) liquid crystal panel, The answer speed can be significantly improved.

The electro-optical display device using the cyclohexane compound of the present invention can be used for applications such as watches, calculators, measuring instruments, automobile instruments, copiers, cameras, OA equipment, portable personal computers, mobile phones, etc. it can. Moreover, it can be used also for other uses, for example, a light control window, an optical shutter, a polarization exchange element, and the like.
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited at all by the following examples.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited at all by the following Examples and the like.
The percentages are by weight. All temperatures are given in degrees Celsius.

In the following compound displays, the carbon number of the alkyl group may be represented by a numeral, H may represent a cyclohexane ring, K may represent a keto group, F may represent a fluoro group, and V may represent a vinyl group. The following is an example.

５００ｍＬ容のナスフラスコに３ＨＫＨ３を３．９７ｇ（１５ｍｍｏｌ）入れ、フラスコ内をアルゴン置換し、メタノール（超脱水、和光純薬工業株式会社製）１９０ｍＬで溶解した。反応系を０℃以下とし、ＮａＢＨ_４（キシダ化学株式会社製）の結晶を０．８５ｇ（１．５等量、２２．５ｍｍｏｌ）加えた。３０分後、ＴＬＣで反応の進行を確認し、４０分後にイオン交換水で失活させた。反応系から溶媒を溜去した後、ＣＨ_２Ｃｌ_２で３回抽出し、得られた抽出液をＮａ_２ＳＯ_４で乾燥し、ＣＨ_２Ｃｌ_２を溜去し、真空乾燥を行った。得られた粗生成物をカラムクロマトグラフィー（内径４ｃｍ、シリカゲル１２０ｇを２１ｃｍ高さに充填、ヘキサン：酢酸エチル＝１５：１の混合溶媒を２０ｍＬずつ分注）にて精製し、アキシアル−アルコール（１ａ）（エカトリアル−アルコール（１ｂ）を２％含む）２．０７１ｇ、エカトリアル−アルコール（１ｂ）１．０３９ｇ、両者の混合物０．８６９ｇを得た（合計３．９８ｇ）。 1. Synthesis of alcohol as raw material

3.97 g (15 mmol) of 3HKH 3 was placed in a 500 mL eggplant flask, the inside of the flask was purged with argon, and dissolved in 190 mL of methanol (super dehydrated, manufactured by Wako Pure Chemical Industries, Ltd.). The reaction system was cooled to 0 ° C. or less, and 0.85 g (1.5 equivalents, 22.5 mmol) of crystals of NaBH ₄ (manufactured by Kishida Chemical Co., Ltd.) was added. After 30 minutes, the progress of the reaction was confirmed by TLC, and after 40 minutes, the reaction was quenched with deionized water. After distilling off the solvent from the reaction system, extraction was performed 3 times with CH ₂ Cl ₂ , the obtained extract was dried over Na ₂ SO ₄ , CH ₂ Cl ₂ was distilled off, and vacuum drying was performed. The obtained crude product is purified by column chromatography (inner diameter: 4 cm, packed with 120 g of silica gel to 21 cm height, and 20 mL each of mixed solvent of hexane: ethyl acetate = 15: 1 dispensed), and axial-alcohol (1a ) (Containing 2% of equatorial alcohol (1 b)), 1.039 g of equatorial alcohol (1 b), and 0.869 g of a mixture of the two (total 3.98 g).

エカトリアル−アルコール（１ｂ） 無色結晶 融点６０℃

Axial-alcohol (1a) colorless crystals Melting point 134 ° C

Equatorial alcohol (1b) colorless crystals Melting point 60 ° C

エカトリアル−フッ素化誘導体（４）
５０ｍＬ容のナスフラスコにエカトリアル−アルコール（１ｂ）を１．０７ｇ（４ｍｍｏｌ）入れ、フラスコ内をアルゴン置換し、ＣＨ_２Ｃｌ_２（超脱水、和光純薬工業株式会社製）１０ｍＬで溶解した。反応系を−７８℃以下冷却後、三フッ化Ｎ，Ｎ−ジエチルアミノ硫黄（ＤＡＳＴ）０．８ｍＬ（１．５等量、６ｍｍｏｌ、和光純薬工業株式会社製）を滴下し、室温まで昇温して撹拌した。１時間後、ＴＬＣで反応の進行を確認し、１時間３０分後に５％ＮａＨＣＯ_３水溶液で失活させた。これをＣＨ_２Ｃｌ_２で３回抽出し、得られた抽出液をＭｇＳＯ_４で乾燥し、ＣＨ_２Ｃｌ_２を溜去し、真空乾燥を行った。得られた粗生成物をカラムクロマトグラフィー（内径４ｃｍ、シリカゲル１２０ｇを２１ｃｍ高さに充填、溶媒としてヘキサンを２０ｍＬずつ分注）にて精製し、アルケン体０．１０６ｇ、エカトリアル−フッ素化誘導体（４）とアキシアル−フッ素化誘導体（５）との混合物０．５９３ｇ（５７％）、エカトリアル−フッ素化誘導体（４）０．２２０ｇ（２０％）を単離した。 2. Synthesis of mono-fluorinated derivatives

Equatorial-fluorinated derivative (4)
In a 50 mL eggplant flask, 1.07 g (4 mmol) of equatorial alcohol (1 b) was placed, and the inside of the flask was purged with argon, and dissolved with 10 mL of CH ₂ Cl ₂ (super dehydrated, manufactured by Wako Pure Chemical Industries, Ltd.). After cooling the reaction system to -78 ° C or lower, 0.8 mL (1.5 equivalents, 6 mmol, Wako Pure Chemical Industries, Ltd.) of trifluorinated N, N-diethylaminosulfur (DAST) is added dropwise, and the temperature is raised to room temperature. And stirred. After 1 hour, the progress of the reaction was confirmed by TLC, and after 1 hour and 30 minutes, it was quenched with 5% aqueous NaHCO ₃ solution. This was extracted 3 times with CH ₂ Cl ₂ , the obtained extract was dried over MgSO ₄ , the CH ₂ Cl ₂ was distilled off, and vacuum drying was performed. The obtained crude product is purified by column chromatography (inner diameter: 4 cm, packed with 120 g of silica gel to 21 cm height, and dispensed with 20 mL of hexane as a solvent), 0.106 g of alkene, equatorial fluorinated derivative (4 ) And a mixture of axial-fluorinated derivative (5), 0.593 g (57%) and 0.220 g (20%) of equatorial-fluorinated derivative (4) were isolated.

Equatorial-fluorinated derivative (4) colorless oil

3. Structural Determination of Monofluorinated Derivative The structural determination of the equatorial-fluorinated derivative (4) was performed based on the NMR data shown in FIG. 6 (FIG. 1).
^{In 19} F-NMR, a doublet peak was observed at -174 ppm, and it was confirmed that fluorine was introduced into the compound. Further, it was considered that fluorine was introduced into this compound, as a carbon peak such that doublet (J = 173 Hz) fluorine was added to 93.1 ppm was confirmed by ¹³ C-NMR. Furthermore, in ¹ H-NMR, a peak is observed at (1H, dtd, J = 50, 10.5, 4.7 Hz) at 4.34 ppm on the low magnetic field side, and fluorine has a large coupling constant of 50 Hz on the same carbon. It is believed that the hydrogen is in an axial conformation from the bonding constant, and the fluorine is in an equatorial conformation. From the above results, the structure was determined to be an equatorial-fluorinated derivative (4).

(Example 1, Example 2, Comparative Example 1)
Among compounds of the formula (2), compounds of the formulas (2-1) to (2-3) shown below were uniformly mixed. Equally mixing means that the three compounds are mixed at the same weight. Samples obtained by mixing “each compound shown in the following Table 1”: “a mixture consisting of the above (2-1) to (2-3)” in a weight ratio of 25:75 respectively are Example 1, Example 2, Comparative Example It is assumed to be 1.

  The response speed in Table 1 above is the result of measurement with a cell gap of 3 μm vertical gradient cell at an applied voltage of 10 Volt, a frequency of 60 Hz and a square wave of 300 msec. The fall time refers to the time until the dielectric constant changes 50% from the maximum dielectric constant when the voltage is off. Table 1 shows each in millisecond (msec). By reducing this time, the response speed is improved.

(Example 3, Example 4, Comparative Example 2)
Among the compounds of the formula (2), the compounds shown in the following table were mixed at the mixing ratio shown in the following table.

Samples obtained by mixing “each compound shown in Table 2 below”: “mixture shown in Table 7” at a weight ratio of 20:80 are respectively referred to as Example 3, Example 4 and Comparative Example 2.

  The response speed in Table 2 is the result of measurement in a TN cell with a cell gap of 4 μm at the time of application of an applied voltage of 10 V and a frequency of 60 Hz. The fall time refers to the time until the dielectric constant changes 50% from the maximum dielectric constant when the voltage is off. In Table 2, all are represented by millisecond (msec). By reducing this time, the response speed is improved.

(Example 5, Example 6)
The residual ratio of 2 samples of 3HFH3 (equatorial body alone) and 3HFH3 (equatorial body / axial body = 7/3 mixture) after storage in a gear oven at 100 ° C. for 1 hour was confirmed by HPLC. The equatorial body has a significantly higher heat resistance than the axial body.

  The liquid crystal composition according to the present invention has an improved response speed, particularly in a TN (Twisted Nematic) mode, a VA (Vertical Alignment) mode, and an IPS (In-Plane-Switching) mode. Providing a liquid crystal panel, the industrial applicability is extremely high.

Claims (7)

As the first component, the following formula (1)

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)
Containing at least one compound of the cyclohexane compound group represented by
Formula (2) as a second component

(In the formula (2),
R ³ and R ⁴ independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 11 carbons, or any hydrogen is fluorine And C 2-12 alkyl or alkenyl substituted with
X ¹ and X ² are independently fluorine or chlorine,
Z ¹ and Z ² are independently methyleneoxy, carbonyloxy, ethylene or a single bond,
n is 0, 1 or 2;
m is 0 or 1;
p is 0, 1 or 2;
q is 0, 1, 2 or 3; )
A liquid crystal composition comprising at least one compound of each compound group represented by The following formula (3) below the trace amount as the first component

(In the formula ^{(3), R 1 (e} ), R 2 (e) is, ^R 1 (e) in each equation ^(1), has the same meaning as ^R 2 (e), X (a) is axial position Represents a halogen atom substituted by
The liquid crystal composition according to claim 1, containing at least one compound of the cyclohexane compound group represented by Following formula (4)

(In formula (1), R ¹ and R ² are the same or different and each represents R, ROCO, RCOO, and R represents an alkyl group, an alkenyl group or an alkynyl group. The alkyl group, the alkenyl group or the alkynyl group. May be substituted by a halogen atom or a cyano group, and part of CH ₂ groups in the alkyl group, alkenyl group or alkynyl group may be replaced by -O-, -CO- or -COO- X and Y each independently represent the same or different halogen atom, or X represents an oxygen atom, and Y represents a direct bond to the oxygen atom.)
Further comprising at least one compound of the cyclohexane compound group represented by
The liquid crystal composition according to claim 1. The following formula (1) for producing a liquid crystal composition

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)
Use of a cyclohexane compound represented by   An electro-optical display element in which the liquid crystal composition according to any one of claims 1 to 3 is sealed in a liquid crystal cell.   The electro-optical display device according to claim 5, which is a liquid crystal panel of a TN (Twisted Nematic) system, a VA (Vertical Alignment) system, or an IPS (In-Plane-Switching) system. The following formula (1) for manufacturing an electro-optical display element

(In formula (1), R ¹ (e) and R ² (e) are the same or different and each represents R, ROCO or RCOO substituted at the equatorial position, R represents an alkyl group, an alkenyl group or an alkynyl group The alkyl group, the alkenyl group or the alkynyl group may be substituted by a halogen atom or a cyano group, and a part of CH ₂ groups in the alkyl group, the alkenyl group or the alkynyl group is —O—, —CO It may be substituted by-or -COO-, and X (e) represents a halogen atom substituted at the equatorial position.)
Use of a cyclohexane compound represented by

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